Lubricant composition containing naphthenic acid esters of polymeric polyhydric alcohols



product. "Dr, desired,'1the reaction canbe carried out 2,970,966 Praised Fe -F United States Patent an ce l the-polymermolecule and thenumber of hydroxyl groups ,970,950 in the polymer molecule can be regulated, greater proportions of monofunctional reactant providing lesser molecular weights andhydroxyl groups. per molecule and vice 5 versa.

LUBRICANT COMPOSITION CONTAINING NAPHQ THENIC ACID ESTERS or POLYMERIC POLY- HYDRIC ALCOHDLS "The; monofunctional reactant can be reactive either u Jolly, k .,pa assignmqs i] with theTpolyhydric phenol or the other polymer-forming (Company, Philadelphia, Pa.,,a corporationv of New reactant. Examples of monofunctional reactants reactive Jersey c with. the polyhydric phenol are ethylene chlorohydrin, H i n t V 10 glycerol monochlorohydrin, erythritol monochlorohydrin, g ggg fg 1fl gg if: mannitol monochlorohydrin, sorbitol monochlorohydrin, 1 Divided and thisal'lplicafin NIay 7 1957; I ethylene oxide, propylene. oxide, glycidol, dimethyl suls No' 7 fate, dlethyl sulfate, etc. Examples of monofunctional c reactants reactive with the other polymer-forming reacclalmsin tant are phenol, alkyl phenols, etc.

' V When'phenol is used as monofunctional reactant in the reaction of-bis-phenol and epichlorohydrin, the product obtained is:

This invention relates to naphthenic acidesters of polymeric polyhydric alcohols.

It is known in the art to prepare polymeric polyhydric where n is, for example, 7 alcohols having alternate aliphatic chains: and aromatic In the polymeric alcohols esterified according tothe nuclei united throughether oxygen. ,For-examplqa polyinvention, there are preferably hydroxyalkyl groups and mer represented by the formula; hydrocarbon groups containing aromatic nuclei united CHs 319 iOm-{bCO cmononormIl -oOdOocmomon where n is, for example, 6, can be prepared by reacting 35 through ether linkages. For example, the polymer decpichlorohydrin with bis-phenol (p,p-dihydroxydiplienyl scribed in the preceding paragraph has alternate monodimethyl methane) in the presence of ethylene: chlorohydroxy trir'nethylene groups and diphenyl dimethyl methhydrin and caustic soda, the mole proportions bein'g such ane groups: united by ether linkages between the arothat the epichorohydrin and bis phenol-form the polymatic nuclei and the terminal methylene groups of the mer unit within the brackets in the above formula, and 40 monohydroxytrimethylene groups. The number of cartwomolecules of ethylene chlorohydrin and one molebon atoms in each hydroxyalkyl group is preferably withcule of bis-phenol form the end groups. Various other i the range from 3 to The n e f carbon atoms polymeric polyhydric alcohols of the indicated type can inrthe hydrocarbon group containing the aromatic nube prepared by reacting various polyhydric phenols with cleusor nuclei is preferably within the range from 6 to 20. various epihalohydrins, polyepoxy compounds} or poly- The number of y y E Q P in the Polymeric a100- haloalcohols. hols is generally within the range from 3 to 20.

According to the present invention, naphthenic acid Various p y y P n can be used to P p esters of the polymeric polyhydriealcohols in uestion the polymeric polyhydric alcohols. Examples of suitable are prepared. It has been found that these esters expolyhydric phenols are mononuclear polyhydric phenols jhibitsuflicient dispersibility in 'mineraloils such as luhriu h as r s r i hydrequinene, eateehol, phlereglueieating oils to permit the preparation of valuable mineral e and p ly l ar p lyhydric phenol u h s bis.- oil compositions containing the esters. Generally. greater P P,P" y y p P,P'- hY 'Q Y dispersibilities in lubricating oils can be obtained by using P Y P P" Y yd Y .p, ',p'- r hy r xy ihigher molecu ar weight naphthenic acids in the esterifiph yl dimethyl e. hematoxylin, p y y cationt Preferred average molecular weight-softhe'naphthracenfis, polyhydric naphthalenes,

thcnic acids are those above 300, though naphthenic acids Examples of Suitable epihalohydrins that y b used having lower average molecular weights can be used. are p l epibromohydl'in, epihalohydrins of n In the preparation Ofth olymeri l h d i l h l mannitol, epihalohydrins of sorbitol, epihalohydrins of which are esterified according t theinvention, a polyerythritel. ete. Examples f suitable n y e o s hydr'ic phenol can be reacted withan epihalbfiydrin, a are glycerol dichlorohydrin,beta-methylglyceroldichloropolyepoxy compound,'or'polyhaloalcohol in the absence hydrin, mannitol dichlorohydrin, sorbitol dichlorohydrin. 'pfany other compound which enters into thepol'ymer Examples of suitable polyepoxy compounds are bis-(2,3 epoxypropyl) ether, butylene dioxide, mannitol diepoxide,

fin'fithe presence of a monofunctional reactant which is Sorbitol diePOXide,

"c apable of reacting with only one moleculeof the poly- 5 c The preparation of the polymeric polyhydric alcohols hydric phenol or the other polymer-forming reactanhfile. the iepihalohyd'rin, polyepoxy compound, or polyhaloalcohol. When such, monofiinctional reactantf'is used, it forms the end-groups of the polymer molecules. The

in question is known in the art. Generally, it involves reaction of the polyhydric phenol and other polymer.- forming reactant,,e.g. epichlorohydrin, a monofunctional reactant being present if desired, at an elevated temperause of such monofunctional reactantsis preferred since, 7 mines-a u 0 Co for a bs an i l Per d ftim by" M justment of thernole ratio of monofunctional reacv eg, about 2 hours. ,When the other polymer-forming tant to polyfunctional reactants, the molecularweight of 'reactantcontains halogen atomswhich are split out in ama can reaction, the reaction is generally performed in the presence of a strong base, e.g. caustic soda, which is neutralized after the completion of the reaction, the salt water formed being then removed from the polymer'pr'oduct. The esterification of the polymeric polyhydric alcohol can be accomplished by reacting the alcohol with naphthenic acids at an elevated temperature, e.g. about 200 C. to 300 C., under refluxing conditions with removal of water by means of a water trap. The esterification may be conducted if desired in the presence of an inert gas such-as nitrogen or carbon dioxide. A solvent, e.g. petroleum spirits, can be employed in the esterification if desired. Instead ofnaphthenic acids, the corresponding acid chloride or anhydride can be employed. Approximately stoichiometric amounts of the reactant can be employed, or an excess of either reactant can be employed and the excess reactant separated, e.g.. by distillation, from the ester product. a

The esters of the'invention are useful in a 'variety of applications. .They may be used as components of varnish compositions and other coating compositions, or as components of mineral oil compositins. The esters are used to advantage as components of compositions containing mineral lubricating oil and petroleum sulfonates. Such compositions are well suited for use as slushing oils, lubricating oils, etc. The sulfonates and Any suitable known conditions for polymerization of styrene can be employed. For example, the mixture can be maintained at an elevated temperature, preferably at least 100 C. and preferably at a temperature and pressure such that the styrene is in liquid phase, in the presence of, a polymerization catalyst such as ditertiary butyl peroxide, benzoyl peroxide, hydrogen peroxide, tertiary butyl hydroperoxide', acetylbenzoyl peroxide, tertiary butyl perbenzoate, etc. The use of a catalyst is not strictly necessary, but is preferred according to the invention. The time required to obtain a suitabledegree of polymerization depends on the temperature, and will generally be within the range from 5 to 50 hours.

esters according to the invention impart highly desirable weight of the esters according to the invention. Suitable sulfonates include the sodium, potassium, lithium, calcium, strontium and barium salts of petroleum sulfonates, Alkali metal and alkaline earthmetal sulfonates g'enerally are suitable, as well as 'sulfonates of other metals. Preferred mineral oils for use in the compositions in question are those having S.U. viscosity at 100 F. within the range from 100 to 1600. y

The esters according to the invention can be copolymerized with vinyl aromatic compounds such as styrene to give products having increased resistance to water and alkali. Such copolymerization canbe effected by. contacting the esters and the vinyl aromatic compound'under conditions normally productive of polymerization of the vinyl aromatic compound. The monovinyl aromatic compound employed according to the invention is one having the following formula:

where R is hydrogen, methyl, or ethyl, A is hydrogen or halogen or an alkyl radical having not more than three carbon atoms, and B is hydrogen or halogen or an alkyl radical having not more than three carbon atoms. Examples of suitable monovinyl aromatic compounds are styrene, o-methyl styrene, p-methyl styrene, o-ethyl styrene, p-ethyl styrene, o,p-dimethyl styrene, o,p-diethyl styrene, p-chlorostyrene, m-chlorostyrene, o-methyl-pchlorostyrene, o-ethyl p chlorostyrene, o-methyl-p-isopropyl styrene, alpha-methyl styrene, p-methyl-alpha- :methyl styrene, alpha-ethyl styrene, o,p-dimethyl-alphamethyl styrene, mechloro-alpha-methyl styrene, p-chloroalpha-methyl styrene,"p-isopropyl-alpha-methyl styrene, m-chloro p methyl alpha methyl styrene, mixtures of monovinyl aromatic compounds,.etc. I

The relative proportions of vinyl compound and esters in the copolymerization mixture will generally be in the range from 10 to 150 .parts bywei'ght, preferably 20 to 80 parts by Weight, of vinyl .compound per 100 ,parts of the esters. The vinyl compound is preferably added dropwise to the polymerization mixture during the reaction.

The following examples illustrate the invention:

' Example I Naphthenic acid esters of a bis-phenol epichlorohydrin condensation product were prepared. The naphthenic acids used had saponification number of 217 mg. of KOH per gram and acidnumber of 208 mg. of KOI-I per gram, indicating average molecular weight in the neighborhood of 270. The condensation product used is known by the trademark Epon 1004 and has an average molecular weight of about 1400 and a combining weight of about 174 with monocarboxylic acids, the average number of hydroxyls and potentials hydroxyls per molecule being about eight. Epon 1004 is a hard, amber resin having melting point of about 75-80 C.

grams of naphthenie'acids-and 100 grams of Epon 1004 were reacted at 280 C. in an atmosphere of nitrogen for about 15 hours. The reaction productwas' a homogeneous hard, darker amber resinous material having melting point of about 51-59" C., saponification number of about 105.6, and acid number of about 19.7. The product was found to be dispersible in amounts up to 1% by weight in naphthenic base lubricating oil having S.U. viscosity at 100 F. of about 100 seconds. TheEpon 1004. prior to esterification, on the other hand, is not dispersible to any appreciable extent in such lubricating oil.

This example shows that naphthenic acid esters of bis- .phenol epichlorohydrin condensation products can be prepared, which esters have substantially greater dispersibility in lubricating oil than the condensation product prior to esterification.

1 Example 11 :Anothersample' of the same naphthenic acids used in Example I was reacted with another sample of Epon 1004. -100 grams ofnaphthenic acids, 100 grams of Epon'1004, and 100 grams ofpetroleum spirits were refluxedat C. in an atmosphere ofnitrogen for 21 hours. Spirits were stripped v from. the reaction product at 205 C. to obtain a homogeneous product resembling the product of Example I and having melting point of 48-52 C., saponification numberof 106.4, and acid number of 21.5.

, This example shows that the esterification can be car- ,ried out inthe presence of a solvent with generally similar 1 65111118.

' Example III A reaction product obtained in a manner similar. to thatdescribed in Example 11 was reacted with styrene ,urider' polymerizingflconditions to produce styrenated Qnaphthenicacid esters of, ;abis-phenol epichlorohydrin condensation product. g Asolution of the reaction product in l'00fgramslofspirits was heatedLat 170 C., and 100 grams. of styr'ene containing 3 grams of ditertiary butyl peroxide were added dropwisewith stirring. After'addition of 100 grams of styrene, the reaction mixture was maintainediat 170 C- for 7 hours Solvent and unreacted, styrene .were strippedoffpand the remaining 'produ'ct'jblo'wn with nitrogen; 1 p

,The reaction product-wasa homogeneous, yellow, .brittle solid having melting point of 63-73 C.,=saponifica- "tion number of 73.5, and acid number of 7.9'.

This example shows that naphthenic acid esters of bisphenol epichlorohydrin condensation products can be styrenated to product materials having modified and advantageous properties.

Example IV The following composition was prepared:

Parts (wt.)

Mineral lubricating oil 94 Sodium sulfonates 5 Naphthenic acid ester of Epon 1004 (prepared as described in Example 11) 1 This composition was a stable, homogeneous dispersion of sulfonates and ester in lubricating oil.

The rust-inhibiting properties of this composition were tested by placing a film of the composition on a plate of sand-blasted A.S.T.M. 1020 low carbon steel, and maintaining the latter in an atmosphere of 100% humidity at 100 F. for 300 hours. At the end of this period, no rust was visible on the plate. These results indicate the superior rust-inhibiting properties of the composition.

Naphthenic acid esters according to the present invention include both esters of naturally occurring petroleum naphthenic acids and esters of carboxylic acids obtained by partial oxidation of petroleum hydrocarbon fractions containing substantial quantities, e.g. at least 20 weight percent, and preferably at least a major proportion, of compounds containing at least one naphthene ring. Typical oxidation conditions which may be employed in partial oxidation include: temperature 200 F. to 300 F.; pressure atmospheric to 500 p.s.i.g.; oxidizing agent, air, oxygen, ozone, ozonized air, H 0 etc.; catalyst, if any, of the well known metal oxidation catalyst type, e.g. manganese, naphthenate, etc. If desired, any suitable means can be employed to separate carboxylic acid oxidation products from unoxidized hydrocarbons and from other oxidation products.

This application is a division of copending application 6 Serial No. 394,903, filed November 27, 1953, by the same inventor, now Patent No. 2,868,761, issued January 13, 1959.

The invention claimed is:

1. A new composition of matter consisting essentially of mineral lubricating oil containing 0.1 to 10 weight percent of alkali metal petroleum sulfonates, and having dispersed therein 0.1 to 1.0 Weight percent of petroleum naphthenic acid esters of glyceryl polyethers of polyhydric phenols, which polyethers in unesterified form are not appreciably dispersible in petroleum lubricating oil, said polyethers having alternate hydroxyalkylene radicals and aromatic radicals united through ether oxygen, the hydroxyalkylene groups containing 3 to 6 carbon atoms and the aromatic radicals containing 6 to 20 carbon atoms, said polyethers containing 3 to 20 hydroxyl groups per molecule, and said esters being obtained by reacting said polyethers with naphthenic acids, which acids have average molecular Weight of at least 270, the amount of said acids being in the range from an equal amount by weight to that of said polyethers to a stoichiometric amount for reaction with all hydroxyl groups of said polyethers.

2. Composition according to claim 1 wherein said esters are obtained from naphthenic acids, said acids having average molecular weight above 300.

3. Composition according to claim 1 wherein said aromatic radicals are diphenyl dimethyl methane radicals.

4. Composition according to claim 1. wherein said polyethers have average molecular weight of about 1400.

5. Composition according to claim 1 wherein said polyethers contain about 8 hydroxyl groups per molecule.

References Cited in the file of this patent UNITED STATES PATENTS 2,173,117 Johnson Sept. 19, 1939 2,672,444 Wasson et al Mar. 16, 1954 2,681,315 Tongberg et al June 15, 1954 

1. A NEW COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF MINERAL LUBRICATING OIL CONTAING 0.1 TO 10 WEIGHT PERCENT OF ALKALI METAL PETROLEUM SULFONATES, AND HAVING DISPERSED THEREIN 0.1 TO 1.0 WEIGHT PERCENT OF PETROLEUM NAPTHENIC ACID ESTERS OF GLYCERYL POLYETHERS OF POLYHYDRIC PHENOLS, WHICH POLYETHERS IN UNESTERIFIED FORM ARE NOT APPRECIABLY DISPERSIBLE IN PETROLEUM LUBRICATING OIL, SAID POLYETHERS HAVING ALTERNATE HYDROXYALKYLENE RADICALS AND AROMATIC RADICALS UNITED THROUGH ETHER OXYGEN, THE HYDROXYALKYLENE GROUPS CONTAINING 3 TO 6 CARBON ATOMS AND THE AROMATIC RADICALS CONTAINING 6 TO 20 CARBON ATOMS, SAID POLYETHERS CONTAINING 3 TO 20 HYDROXYL GROUPS PER MOLECULE, AND SAID ESTERS BEING OBTAINED BY REACTING SAID POLYETHERS WITH NAPHTENIC ACIDS, WHICH ACIDS HAVE AVERAGE MOLECULAR WEIGHT OF AT LEST 270, THE AMOUNT OF SAID ACIDS BEING IN THE RANGE FROM AN EQUAL AMOUNT BY WEIGHT TO THAT OF SAID POLYETHERS TO A STOICHIOMETRIC AMOUNT FOR REACTION WITH ALL HYDROXYL GROUPS OF SAID POLYETHERS. 